Benzene hexachloride packaging



Patented Apr. 28, 1959 2,884,128 BENZENE nExAcrnoRIDE PACKAGING Eugene D. Witman, Pittsburgh, Pa., assignor to Columbiw Southern Chemical Corporation, Allegheny County, Pa., a corporation of Delaware No Drawing. Application February 6, 1958 Serial No. 713,557

7 Claims. (Cl. 206--S4)- This invention involves the handling of benzene hex-a chloride, and more particularly deals with the packaging of benzene hexachloride in bags.

Benzene hexachloride, and notably the gamma isomer of benzene hexachloride, is a widely used commercial insecticide. As prepared by additive chlorination of benzene, it is comprised of five isomers, including the desired gamma isomer. This isomer composition and the individual isomers are solid at normal temperatures. In many applications, the insecticidal properties of benzene hexachloride are most advantageously realized by formulation with various diluents or carriers such as inert solids or organic solvents.

Preparation of these formulations is usually accomplished using benzene hexachloride in the form of small solid particles. One such form is known as flaked benzene hexachloride. This refers to a product produced by solidifying molten benzene hexachloride in a thin film on the periphery of a rotating, cooled drum, and stripping or shaving off the solidified film. Benzene hexachloride compositions so prepared are in the form of rather small, quite thin particles, e.g., flakes. Sometimes these flakes are so small as to give a powdery composition. Other particul'ated benzene hexachloride compositions may also be prepared, as by dropping molten benzene hexachloride (or benzene hexachloride solution) into a non-solvent, usually water, and thereby precipitating solid divided benzene hexachloride.

Eflfective handling of particulate benzene hexachloride ganerally requires it be packaged, stored and shipped in convenient, usually small, containers such as bags holding 50 to 100 pounds. However, when paper bags are used, the bags rupture quite quickly, often within about two months. Even with multi-ply cellulosic paper bags and bags having inner plies of synthetic films, bag rupture is encountered to a distressing degree.

According to' this invention, it has been discovered that benzene hexachloride may be packaged in bags, especially paper bags, and stored therein for extensive periods of time, ranging even upwards of about one year, without .bag rupture. This extended bag life is realized by incorporating in the benzene hexachloride a minor concentration of Fan organicepoxide (oxirane compound). The presence of from about 0.1 to 5.0 or more percent epoxide byweight of the composition inhibits or subst'antially retards the tendency of bags containing benzene hexachloride to failure by rupture. Substantially higher epoxide concentrations are not normally used, among other-reasons, because of the expense involved When benzene hexachloride containing an epoxide in a rninorconcentration which inhibits or retards bag rupture '2 is packaged, bag life in excess of six months and often or more than a year is obtained.

The exact manner in which the epoxide is incorpo rated with the benzene hexachloride is the specified con centration can be varied to suit other considerations encountered in the manufacture of the benzene hexachlo ride and the physical properties of the epoxides as hereinafter discussed. Especially suitable results are obtained by blending the epoxide into molten benzene hexachlo ride. In conjunction with'normal manufacturing procedures, this conveniently includes adding the epoxide to benzene hexachloride while it is in molten state during its manufacture. One typical circumstance of this charac ter arises during the purification and recovery of benzene hexachloride from the reaction mixture provided by add ing chlorine to benzene and forming benzene hexachloride. As a rule, a considerable excess of benzene is present and must be removed. This is frequently accomplished by vaporizing the benzene from the benzene hexachloride. Temperatures for such vaporization are such that the benzene hexachloride is molten.

As already outlined, benzene hexachloride is conven= iently oifered for sale as a finely divided solid composition, usually as flaked benzene hexachloride. Flaking results, for example, from solidifying molten benzene hexachloride as a thin layer on the periphery of a rotating, cooled drum, and thereafter scraping the solidified benzene hexachloride on the drums periphery. The detached benzene hexachlorideis flaked. The epoxide may be added to the molten benzene hexachloride prior to distribution on the drums periphery. Molten benzene hexachloride formed during benzene removal may be directly fed to the flaking operation in which case the epoxide is incorporated in the benzene hexachloride after it is melted and before it is flaked.

Improved bag life is also realized by adding the epoxide to benzene hexachloride after it has been solidified as, for example, by dusting flaked benzene hexachloride with the epoxide. This -treatment may simply take the form of mixing the epoxide and particulate benzene hexa: chloride.

Subsequent to the incorporation of the minor effective concentration of epoxide in-the benzene hexachloride with the consequent formation of a solid, particulate benzene hexachloride composition, the composition is packaged in paper bags (bags primarily of cellulosic materials) for storage, shipment and other conveniences. In many instances, the paper bags are large enough to contain from 50 to 150' pounds of benzene hexachloride. In such sizes, the packaged benzene hexachloride can be shipped, stored and otherwise handled with facility.

By the term organic epoxide as herein used, an organic compound containing an epoxy group is intended. These compounds are often called oxiranes or 1,2-epoxides and contain an oxygen atom linked to both of two adjacent carbon atoms.

In general, it is preferable to employ organic epoxides that are other than gaseous "at room temperature. 'I'hus, organic epoxides having boiling points above 25 C., and notably above about C., are most convenient to use.

Ideal are organic epoxides which are solids at tempera tures to which the packaged benzene hexachloride may be subjected during shipment, handling and storage in the bags.

Depending, of course, upon the particular technique by which the epoxide is incorporated in the benzene hexachloride composition, certain organic epoxides are more appropriate. Thus, if the organic epoxide is added to the molten benzene hexachloride, an epoxide which does not decompose or volatilize substantially at the temperatures of the molten composition is best chosen, among other things, since loss of epoxide is minimized or eliminated. Also, if the particulate benzene hexachloride is to be prepared by precipitation in an aqueous solution or the like, organic epoxides insoluble in the precipitating medium should be used again to conserve epoxide.

Obviously, if the organic epoxide is to be added to the particulate benzene hexachloride, organic epoxides of appropriate physical properties which facilitate retention with the benzene hexachloride are suitably selected.

Aside from selecting an organic epoxide which is best suited for incorporation in the solid particulated benzene hexachloride composition, any organic epoxide is useful in making possible improved bag life. Thus, useful are ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, cyclohexene oxide, cyclopentene oxide, tetrahydronaphthalene oxide, styrene oxide, 4-vinyl cyclohexene oxide, pinene oxide, the mono and polyepoxide of other substituted and unsubstituted aliphatic and cycloaliphatic olefinically unsaturated hydrocarbons such as mono and diepoxides of diisobutylene, butadiene monoepoxide, butadiene diepoxide, epichlorohydrin, epibromohydrin, glycerol and its esters and ethers including the methyl, ethyl, propyl, amyl, dodecyl, phenyl, tolyl, halophenyl (chlorophenyl, bromophenyl), xylyl, alphaor beta-naphthol ethers as well as alkyl and aryl esters of glycidol and carboxylic acids such as acetic, propionic, butyric, oleic, stearic, maleic, phthalic, benzoic, among others; epoxides of olefinically unsaturated acids such as 2,3-epoxy acrylic acid, 2,3-epoxy methacrylic acid, 2,3-epoxy butyric acid, epoxy oleate and their esters as derived from aliphatic, aralkyl and aryl alcohols as illustrated by the methyl, ethyl, propyl, isopropyl, allyl, vinyl, benzoyl, phenyl, glycidol type esters; epoxidized unsaturated fatty acids like oleic and linoleic such as found in corn oil, linseed oil, cottonseed oil, soybean oil.

Also aliphatic diesters of 4,5-epoxycyclohexane-l,2- dicarboxylic acids such as di-(2-ethylhexyl) 4,5-epoxycyclohexane-l,Z-dicarboxylate, didecyl 4,5-epoxycyclohexane-l,2-dicarboxylate, di-(tridecyl) 4,5-epoxycyclohexane-1,2-dicarboxylate, diallyl 4,5-epoxycyclohexane-1,2- dicarboxylate; aliphatic esters and ethers of 3,4-epoxycyclohexylrnethanol such as 3,4-epoxycyclohexylmethyl acetate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethanol, 2-(2-butoxyethoxy) ethyl ether of 3,4-epoxycyclohexylmethanol, 4,5-epoxycyclohexane-1,2- dicarboxylic acid and the corresponding anhydride; allyl 3,4-epoxy-2-hydroxyalkanoates such as allyl 3,4-epoxy-2- hydroxybutanoate, the corresponding pentanoate, and allyl 3,4-epoxy-2-hydroxy-3-methylbutanoate.

The following example illustrates the manner in which this invention may be practiced and the benefits which may be realized:

EXAMPLE In these tests, flaked benzene hexachloride compositions comprising a normal additive chlorination isomeric mixture and a specified concentration of epoxide is packaged in sealed paper bags which are, thereafter, stored under representative storage conditions. Each bag contains about 70 pounds of isomeric benzene hexachloride. The bag is a five ply natural kraft paper bag.

" Each bag is periodically inspected and their appearance and strength ascertained. If, upon reasonable handling, the bag breaks, or is discovered to be ruptured under storage conditions, this is considered bag failure.

The following is a tabulation of benefits which may be obtained:

Table DESCRIPTION OF BAGGED COMPOSITION Concentration, Weight Percent Test Epoxide Comments Bag fails in about 60 days. Bag satisfactory after 6 months. Bag satisfactory after 9 months.

D0. Bag satisfactory after 6 months. Bag satisfactory after 9 months.

Do. Do. Do.

Do. Bag satisfactory after 6 months.

nonc

cyclohexene oxide vinyl ester of epoxyoleate phenyl ether of glycidol epichlorohydrin phenoxypropene oxide alpha-naphthoxypropene oxide. dimethyl glycide phenylmethyl glycide butadiene monoxidem 2,3-epoxybutyric acid allyl 2,3-cp0xybutyratc epoxidized soybean oil The present invention is applicable to the packaging in paper bags of benzene hexachloride including the individual isomers as well as various isomeric mixtures. Of course, its use is mainly in conjunction with isomeric mixtures of benzene hexachloride encountered in the addition chlorination of benzene. Thus, isomeric mixtures provided by the additive chlorination of benzene at temperatures from minus C. to 70 C. are most frequently packaged. The isomeric mixture realized by additive chlorination of liquid benzene from which has been separated the solid benzene hexachloride that precipi'tates after substantial benzene conversion may also be packaged in this process. Removed isomers are mainly the alpha and beta isomers under such circumstances. Such benzene hexachloride compositions are comprised substantially of isomers of benzene hexachloride except for impurities present as an incident to their manufacture.

Although the present invention has been described with reference to specific details of certain embodiments, it is not intended that it be construed as limited thereto except insofar as such limitations appear in the appended claims.

I claim:

1. A method of packaging solid benzene hexachloride which comprises forming a composition of solid, finely divided benzene hexachloride containing a minor concentration of at least 0.1 weight percent of an epoxide and packaging the composition in a paper bag.

2. A method of packaging solid benzene hexachloride which comprises adding a minor concentration of at least 0.1 Weight percent of an epoxide to benzene hexachloride subsequent to the formation of benzene hexachloride and thereafter packaging the benzene hexachloride as a solid composition in a paper bag whereby to obtain a bagged product of extended bag life.

3. The method of claim 2 wherein the epoxide is a solid.

4. A method of packaging solid benzene hexachloride which comprises forming a molten benzene hexachloride composition, adding an epoxide thereto to provide a minor concentration of at least 0.1 percent epoxide by weight, solidifying the molten composition and packaging solidified product in a paper bag.

5. The method of claim 4 wherein the composition is from 0.1 to 5.0 percent.

6. A benzene hexachloride package comprising a sealed paper bag containing finely divided benzene hexachloride having dispersed therein an epoxide in a minor concentration of at least 0.1 percent by weight effective to improve the life of the package.

7. A benzene hexachloride package comprising a sealed paper bag containing finely divided benzene hexachloride having dispersed therein an epoxide in a minor concentration of from 0.1 to 5.0 weight percent effective to improve the life of the package.

References Cited in the file of this patent UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 2,884,128 April 28, 1959 Eugene D, Witman of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 44, for "generally" read generally line 61, for "failure" read fail column 2, line 1, for "often or" read often of line 4, for is the" read in the column 6, line 3, beginning With "References Cited" strike out all to and including "Augo 6, 1957" in line 5, same column,

Signed and sealed this 22nd day of March 1960,,

(SEAL) Attest:

ROBERT C. WATSON Commissioner of Patents KARL Ho AXLINE Attesting Ofiicer 

6. A BENZENE HEXACHLORIDE PACKAGE COMPRISING A SEALED PAPER BAG CONTAINING FINELY DIVIDED BENZENE HEXACHLORIDE HAVING DISPERSED THEREIN AN EPOXIDE IN A MINOR CONCENTRATION OF AT LEAST 0.1 PERCENT BY WEIGHT EFFECTIVE TO IMPROVE THE LIFE OF THE PACKAGE. 